Quaternary salts of c-vinylpyridine polymers with compounds containing a haloacetyl group



Feb. 21, 1961 'r. M. LAAKSO EI'AL 2,

QUATERNARY SALTS 0F C-VINYLPYRIDINE POLYMERS WITH COMPOUNDS CONTAINING A HALOACETYL GROUP Filed Sept. 3, 1957 EMULSION I PsL/PPORT AMT/STATIC LAYER GROUP.

ThomasMLaa/tso JackLR.Williams Cabin 6! Garber INVENTORS' WiM ATTORNEYIS JIG'ENT 2,972,535 QUATERNARY SALTS F C-VINYLPYRIDINE POLYMERS WITH COMPOUNDS CONTAIN- lNG A HALOACETYL GROUP Thomas M. Laakso, Garber, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New v Jersey Filed Sept. 3, 1957, Ser. No. 681,601 12 Claims. 01. 96-87) ,This invention relates to salts of vinylpyridine polymers, and moreparticularly to quaternary salts of C- vinylpyridine polymers with certain organic compounds containing a halogen-substituted acetyl group and more especially a chloroacetyl group, to materials prepared therewith, and to processes for preparing such polymeric salts and materials. The new class of resinous polymers of the invention are derived from C-vinylpyridine polymers by reaction with certain quaternizing agentsin such proportions that the resulting polymer consists from 70 to approximately 100% by weight in linear quaternized units represented by the following general structure:

wherein n represents a whole number and indicates the unit recurs, Y represents an-atom of hydrogen or an alkyl group of 1 to 4 carbon atoms, X represents a halogen atom such as chlorine or bromine, and A represents a member selected from the group consisting of -R which represents, an alkyl group of 1 to 4 carbon atoms, a phenyl group or a substituted phenyl group e.g. methyl, ethyl, propyl, isopropyl, butyl, phenyl, monohydroxyphenyl, dihydroxyphenyl, acetamidophenyhetc. groups, an alkoxy group -OR wherein R represents an alkyl group of from 1 to 24 carbon atoms e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, decyl, dodecyl, hexadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, behenyl, carnaubyl, etc. groups, and an amino group .NR R wherein R represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms and R represents a hydrogen atom, or an alkyl group of 1 to 4 carbon atoms or a phenyl group. The above defined polymeric quaternary salts are film-forming and have numerous uses, but are particularly valuable as antistatic coatings on sheet materials such as light-sensitive photographic films to prevent static markings and other defects produced by friction in the manufacture, use and processing of the same. Each of the classes of compounds coming within the above structure have their own individual characteristics as to their antistatic efiicacy. Thus, a particu-' lar species may be preferred for one type of photo graphic application whereas for a different photographic application another species may be more adapted- They are also efiicacious antistatic coating materials for thin wrapping materials especially for those wherein the sheet material. is a cellulose organic ester. i

It is, accordingly, an object of thisinvention toprovide a new class of polymericv compounds. A more' spe cific object is to, provide new polymericsalts.

character and more particularly photographic. filmsthaf 7 Another ob ect is to provide sheet materialsthat are-.antl'static i'n' Jack L. R. Williams, and Calvin 's. l

combination of recurring 1 r used in substantial excess.

are static resistant. Another object is to provide processes for preparing such polymeric salts and coated materials prepared therewith. Other objects will become apparent hereinafter.

In accordance with the invention, we prepare the polymeric quaternary salts which consist of from 70 to approximately by weight in linear combination of recurring quaternized unitsof the following general struc ture:

wherein n, Y, X and R are as above defined, the remainder of the polymer molecule being residual C-vinylpyridine units, by reacting a resinous C-vinylpyridine polymer with a haloketone, in a solvent medium such as methanol, ethanol, dioxane, etc., at an elevated temperature but preferably at or near the reflux temperature of the reaction mixture, until the resulting viscous dope is completely water-soluble, and then isolating the polymeric salt by precipitating the solution into a larger volume' of a non-solvent such as diethyl ether, petroleum ether, etc., followed by'filtering and drying the polymeric salt; The proportions of the reacting components can vary from equimolar quantities to an excess of one or the other, but, preferably the haloketone component is Typical haloketones that can be usedadvantageously in the-above reaction include halogen substituted ketones such as chloroacetone, bromoacetone, 'chloromethyl ethyl ketone, .bromomethyl ethyl ketone, v -chloroacetophenone, p-chloroacetophenol, pchloroacetylacetanilide, chloroacetopyrocatechol, etc., and the corresponding bromine derivatives wherein a'bromine' atom replaces the chlorine atom in each instance. The polymeric salts prepared with the haloketones wherein R is an alkyl group are outstanding in antistatic characteristics and are preferred.

- To obtain the polymeric quaternary salts of the invention which consist of from 70 to approximately 100% by-weight in linear combination of recurring quaternized units'of the following general structure:

pyridine units, by reacting a resinous C-vinylpyridine polymer with an alkyl ester of chloroacetic or bromoacetic acid, under conditions that are generally similar to those set forth for the preparation of the polymeric salts. represented by above structure 1'. Typical alkyl esters of chloroacetic and bromoacetic acids that can be used advantageously include methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, isopropyl chloroacetate, the butyl chloroacetates, the hexyl chloroacetates, the decyl chloroacetates, the dodecylv chloroacetates, the hexadecyl chloroacetates, the octadecyl chloroacetates the eicosyl chloroacetates, the carnaubyl chloroacetates, etc., and the corresponding esters of bromoacetic acid. In general, the. normal alky esters are preferred. The above-mentioned esters can be prepared by reacting chloro'ac'etyl chloride or"bromo'acetyl chloride with the appropriatesaturatedmonohydroxy alkanol, or by'reacting chloroacetio on bronroacetlc acid with the alkanol' in the presence of a wherein n, Y, X, R and R are as above defined, the remainder of the polymer molecule being residual C- vinylpyridine units, by reacting a resinous C-vinylpyridine polymer with a halogen-containing amine compound having the formula XCH CONR R under conditions that are generally similar to those set forth for the preparation 'of the polymeric salts represented by above structure I. 4

Typical halogen-containing amine compounds that can be used advantageously include chloroacetamide, u-ChlO- ro-N methylacetamide, a-chloro N butylacetamide, achloro,N,N-diethylacetamide, a-chloro-N-ethylacetanilide, 'u-chloro-N-butylacetamide, a-chloro-N-phenylacetamide (a-chloroacetanilide), a-chloro-N-ethylacetamide (CL-Chloro-N-ethylacetanilide), etc. and the corresponding bromine substituted acetamides. While all of the polymeric salts obtained by the above process have excellent anticoating layer over the sensitive emulsion layer to give antistatic properties to the photographic film. However,

static characteristics, those prepared with chloroacetamide,

bromoacetamide and the N-alkyl and N,N-dialkyl derivatives. thereof are outstanding and are preferred.

The intermediate C-vinylpyridine polymers employed for the preparation of the polymeric salts of structures I, II and Ill may be prepared by conventional polymerization methods wherein a monomer such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5- vinylpyridine, etc. is heated in the presence of a polymerization catalyst such as benzoyl peroxide, acetyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, etc., inmass, in solution in an inert organic solvent or polymerizing in emulsion form in a non-solvent 'such as water, the resulting polymers being separated from the polymerization reaction mixture by conventional as indicated in the drawing-application of the polymeric salts to the back of the film, i.e., to the opposite side from that of the sensitive emulsion layer, is preferred.

The following examples'will serve to illustrate further the preparation of the polymeric salts of the invention 'and the application of the same to the product of light-sensitive films having excellent antistatic properties.

, EXAMPLE 1 1 323 g. (3.07 moles) of poly-4-vinylpyridine [{1 }=1.22] were dissolved in 2000 cc. of methyl alcohol by stirring at room temperature. Then, there were added to the viscous solution 420 'g. (4.5 moles) of chloroacetone, and the mixture was heated .atreflux temperature for 24 hours,

- after which time the dope was completely water-soluble.

After dilution with 1 liter of methyl alcohol, the resulting quaternary salt was precipitated from solution in several volumes of diethyl other. I The brittle, light-buff colored solid was leached with 2 changes of ether and dried over P 0 at reduced pressure. The yield of prodnot was 535 g. equivalent to about 88% of the theoretical value. Analysis of this product showed that it contained by weight 57.8% of carbon, 6.2% of hydrogen, 7.5% of nitrogen and 16.8% of chlorine compared with calculated for C I-l NOCl of 60.7%, 6.0%, 7.1%, and 17.9%, re spectively. This result indicated that the product consisted of approximately 87% by weight of recurring units of the following structure:

the remainder of the polymer molecule being residual mean s'such as precipitating or coagulating, filtering, wash- I ing and drying." If desired,'the' intermediate polymers may be copolymers of the above-mentioned C-vinyl'-' pyridines with a lesser quantity by weight of certain other polymerizable monomers such-as styrene, acrylic acid esters and amides including N-alkyl amides, and ot-alkyl substituted acrylic esters and amides including N-alkyl amides, e.g. methyl acrylate, methyl methacrylate, acrylamide, N-methyl acrylarnide, N-methyl methacrylamide, N,N-dimethyl acrylamide, etc. However, the polymeric quaternary salts of the invention prepared from the homopolymers of C-vinylpyridines are preferred.

The accompanying drawing is a sectional view of a photographic film base 1 composed of a hydrophobic material such as a cellulose derivative, e.g., cellulose acetate,

cellulose propionate, cellulose acetate-butyrate, cellulose nitrate, etc., a polyamide such as nylon, a polyester such aspolyethylene terephthalate, polycarbonates, polyethylenes, polypropylenes, and the like, has coated thereon a polymeric salt of the invention as layer 2, and on the opposite side a layer 3 of a light-sensitive material, e.g.,; a gelatine-silver halide emulsion. The layer 2 of the polymeric salt may also have therein a substantial proportion of gelatine, if desired. Although the preferred method of employing the polymeric salts of the invention is in theform of a backing layer as shown in the. drawing, thepolymeric salts can also be incorporated directly inthe sensitive emulsion layeror used asqan over-i 'the example, to give products recurring '4-vinylpyridine units. This product I showed e'x'-' cellent antistatic characteristics when coated on thin wrapping materials and'photographic films.

v In place of the chloroacetone in the above example, there maybe substituted an equivalent amount of related compounds, e.g. bro'rnoacetone, u-chloroacetophenone, c:- bro'r'noacetophenon'e or nuclear substituted u-chloro or ebromoacetophenones wherein the substituent on the phenyl nucleus is an alkyl group of 1 to 4 carbon atoms, a. halogen atom, a hydroxyl group, an amino group, an autamido, group,,etc., to give the corresponding polymeric quaternary salt products having generally similar proper ties, Also, in place of the 'poly-4-vinylpyridine' in the above example, there may be substituted a like amount of poly-2-vinylpyridine or any other of the mentioned 0- vinylpyridine polymers, the reaction therewith being carried out with any of the quaternizing agents mentioned in having generally similar properties.

The above described polymers are capable of further modification by condensation through the carbonyl group with various hydrazones, oximes, hydrazides, semicarbazones and aldehydes'. This kind of process may be better understood by reference to copending applications of T. M. Laakso and J. L. R. Williams, Serial No. 681,603 and Serial No. 681,604, filed of even date herewith, wherein the preparation of certain hydrazide derivatives of the polymeric salt products of the above example are described.

EXAMPLE '2 25 g. (0.238 mole) of poly-4-vinylpyr'idine were dissolved in 450 cc. of methanol by stirring at room temperature. Then g. (0.38 mole) of"'p-chloroacetyl" acetanilide slurried in 250 cc; of methanolwere added.

This. mixture was heated until a test portion of clear,

filtered reaction solution was completely soluble in water.

' "29%; see

The main portion of the viscous solution was filtered to remove the unreacted quaternizing agent. The clear, viscous filtrate was precipitated into 4 liters of diethyl ether, the precipitate of polymeric salt was separated, leached with fresh ether and dried at reduced pressure. A yield of 74.5 g., equivalent to 97% of theoretical value of the polymeric salt product was obtained. Analysis- O O. CHA NHAM.

The product showed good antistatic properties.

In place of the poly-4-vinylpyridine in the above example, there may be substituted a like amount of poly- 2-vinylpyridine or any other of the mentioned C-vinylpyridine polymers. Also, the p-chloroacetylacetanilide in the above example may be substituted by an equivalent amount of p-bromoacetylacetanilide. These additional products likewise show satisfactory antistatic properties when coated on thin wrapping materials and photographic films.

EXAMPLE 3 21 g. (0.2 mole) of poly-4-vinylpyridine beads {{11} 1.28] were dissolved in 600 cc. of dimethylformarnide. To this solution, there were added 40 g. (0.21 mole) of chloroacetopyrocatechol in 100 cc. of dimethylformamide. After standing at 25 C. for 24 hours, the reaction mixture was water-soluble. The polymeric salt was isolated by precipitating the mixture into diethyl ether, followed by filtering, washing and drying the precipitated product. A yield of 55 g. of an amber-colored product, equivalent to 95% of theory was obtained. Analysis showed that the product contained by weight 61.7% of carbon, 4.8% of hydrogen, 4.8% of nitrogen and 12.2% of chlorine compared with calculated for C H NOIO of 60.2%, 6.0%, 7.9% and 9.7%, respectively. On the basis of the chlorine content, this result indicates that the product, poly-4-vinylpyridinium chloroacetopyrocatechol, consisted of approximately 80% by Weight of recurring units of the following structure:

the remainder of the polymer molecule being residual recurring 4-vinylpyridine units.

In place of the poly-4-vinylpyridine in the above example, there may be substituted a like amount of poly 2-vinylpyridine or any other of the mentioned C-vinylpyridine polymers to give generally similar polymeric salt products. Also, the chloroacetopyrocatechol in the above example, may be substituted by related quaternizing agents such as chloroacetoresorcinol, p-chloroacetophenol, etc. and by corresponding bromo derivatives. In addition to their antistatic properties, these polymeric salts function also as non-diffusable photographic developers, as polymeric color couplers and mordants, as Well as antistain, dispersing andwettingagents. For example,

6 an aqueous solution of poly-4-vinylpyridinium chloroacetopyrocatechol reduced freshly prepared Tollins reagent (an'ammoniacal solution of silver oxide), and produced deep colors with various color developers using hydrogen peroxide as oxidizing agent.

The physical properties of the above polymeric quaternary salts may be adjusted by degreeof quaternization or by selecting suitable starting copolymers of the C- vinylpyridines such as previously mentioned. These polymeric quaternary salts are further capable of modification through the functional groups,-for example, insolubilization by a cross-linkingreaction with formaldehyde, bismethanesulfonoxy derivatives of polyglycols, bis developers,.bis azides, and his diazonium coupling agents.

7 EXAMPLE, 4.

323 g. (3.07 moles); of poly-4 vinylpyridine H1 51.22] were dissolved in 2000' cc. of methanol by stirring at room temperature. To this, viscous solution, there were added 555 g. (4.5 moles) of ethyl chloracetate, and the, mixture heated at reflux temperature for 24 hours, after which time the dope was completely watersoluble. After dilution with. 1 liter of methanol, the quaternary salt was precipitated from solution in several volumes of diethyl ether. The brittle, light-buff colored solid obtained was leached in two changes of ether and dried over P 0 at reduced pressure. The yield of product was 585 g. or approximately 84%v of the theoretical amount. Analysis showed that this product contained by weight 55.4% of carbon, 6.6% of hydrogen, 6.7% of nitrogen and 15.3% of chlorine compared with calculated for C H O NCl of 58.4%, 6.1%, 6.1% and 15.6%.- respectively. This result indicated that the product was essentially poly-4-vinylpyridinium ethylchloroacetate consisting of recurring units of the following structure:

This product showed excellent antistatic properties when coated on thin wrapping materials and photographic films.

In place of the poly-4-vinylpyridine in the above example, there may be substituted a like amount of poly- 2-vinylpyridine or any other of the mentioned C-vinylpyridine homopolymers and cop'olymers to give resinous products having generally similar properties.

EXAMPLE 5 g. (0.94 mole) of poly-4-vinylpyridine [{1 }='l.28]- were dissolved in 800 cc. of methanol at room temperature. Then 225 g. (1.5 moles) of n-butyl chloroacet-ate were added to the viscous solution and this mixture was heated at 5055 C., until it became water-soluble (about 24 hours). The resulting quaternary salt was precipitated from solution. in 4 liters of diethyl ether. The brittle, amber-colored solid obtained was leached in 2 changes of fresh ether and dried over P 0 at reduced pressure. The yield of poly-4-vinylpyridinium n-butyl chloroacetate was 205 g. or. equivalent to 84.7%. of the theoretical value. It showed satisfactory antistatic properties when coated on thin wrapping materials and photographic films.

EXAMPLE 6 100 g. (0.95 mole) of poly-4-vinylpyn'dine and 183 g. (1.1 moles) of ethyl-bromoacetate were reacted together in 750 cc. of methanol by Warming at 50 C. until a watersoluble product was obtained. The product was isolated by precipitating into 5 liters of diethyl ether followed by filtering, leaching in fresh ether, and drying. A yield, of 257 g. equivalent to 96.5 of theory of the quz'lterna rfy salt was obtained. Analysis of this product showed that it contained by weight 47.8% of carbon, 5.5% of hydrogen, 5.2% of nitrogen, and 25.8% of bromine compared with calculated theory for C H O NBr of 48.5%, 5.1%, 5.1%, and 29.4%, respectively. No conductivity data were available at this time. This result indicates that the product consisted of approximately 88% by weight of recurring 4-vinylpyridinium ethyl bromoacetate units and 12% by weight of residual recurring 4-vinylpyridine units. The product showed excellent anti static properties when coated on thin wrapping materials and photographic films.

EXAMPLE 7 47.8 g. (0.4 mole) of poly-2-methyl-S-vinylpyridine and 90.7 g. (0.54 mole) of ethylbromoacetate were reacted together in 200 cc. of methanol in similar manner as described in above Example 6. A yield of 85% of the quaternarysalt product was obtained. It consisted of approximately 90% by weight ofrecurring 2-methyl-5- vinylpyridinium ethyl bromoacetate units and by weight of residual recuring 2-methyl-5-vinylpyridine units. The product showed satisfactory antistatic properties when coated on thin wrapping materials and photographic films.

EXAMPLE 8 270.5 g. (1 mole) of l-octadecanol and 94.5 g. (1 mole) of chloroacetic acid in 1 liter of benzene plus 1 drop of H 80 were refluxed 16 hours in a 3-liter, 3- necked flask equipped with an 18-inch glass column topped by an esterification head, and a stirrer and heated by an immersion electric heater. After this interval, the benzene layer was separated, washed with water and then with sodium carbonate solution, followed by final Washing with water. The benzene was removed by fractional distillation leaving a residual oil which after fractionation had a B.P. 210-215 C. at 1 mm. pressure. The colored distillate crystallized to a white solid M.P. 30-32 C. A yield of 320 g. equivalent to 92% of theory was obtained. Analysis showed that this product contained by weight 69.6% of carbon, 11.5% of hydrogen and 10.4% of chlorine compared'with calculated for'C- H O Cl of 69.3%, 11.2% and 10.2%, respectively. This result indicated that essentially pure n-octadecyl chloroacetate had been obtained.

53 g. (0.5 mole) of poly-4-vinylpyridine and 175 g. (0.5 mole) of n-octadecyl chloroacetate prepared as above were refluxed with stirring in 1500 cc. of methanol on a steam bath for 72 hours. The resulting dark-colored solution was precipitated into three volumes of diethyl ether, leached with fresh ether, redissolved in a minimum quantity of methanol, reprecipitated in ether and dried at room temperature under reduced pressure. A yield of 192 g. equivalent to 85 of product was obtained. Analysis showed that this product contained by weight 70.6% of carbon, 8.6% of hydrogen and 8.4% of chlorine compared with calculated for C H NO Cl of 72.0%, 10.2% and 7.9%, respectively. This result indicated that a fully quaternized product, poly-4-1-octadecyl vinylpyridinium chloroacetate, consisted of essentially 100% of recurring units of the following structure:

It showed excellent antistatic properties and greatly improved tackiness when coated on thin wrapping materials and photographic films as compared to the quaternary salts prepared with shorter chain alkyl chloroacetates. Thus, when coated from concentrations of 0.25%, 0.50% and 1.00% in a 60-40 methanol-acetone solution onto a cellulose acetate sheet material and tested for tackiness, the values obtained were less than 10, 10 and 15, respectively. Since a value of 50 or less is considered satisfactory for this test, it will be seen that the quaternary salt of this example has excellent tackiness characteristics. The test for tackiness is really a measure of relative adhesion wherein a roll of film is simulated, i.e. the coated surface is pressed tightly against a similar uncoated sheet of cellulose acetate, and the tension required to strip the films apart is taken as the measure of tackiness.

In place of the n-octadecyl chloroacetate in the above example, there may be substituted an equivalent amount of other long chain esters such as dodecyl, hexadecyl eicosyl, carnaubyl, etc. esters of chloroacetic or bromoacetic acid. These esters may be prepared from the corresponding alcohols by reaction with the said acids as described in the above example. Also, the poly-4- vinylpyridine in the example may be substituted by a like amount of poly-2-vinylpyridiue or any other of the mentioned C-vinylpyridine homopolymers and copolymers. However, the homopolymers are preferred. All of the products mentioned above have generally similar properties as the product of the example.

EXAMPLE 9 100 g. (0.94 mole) of poly-4-vinylpyridine [{1;}=1.28] were dissolved in 800 cc. of methanol at room temperature. Then 178 g. (1.88 moles) of chloroacetamide were added to the viscous solution and this mixture was heated at 4050 C., until it was Water-soluble (usually in 24 hours), after which time the quaternary salt was precipitated from solution in 4 liters of diethyl ether. The brittle, amber-colored solid was leached in two changes of ether and dried over P 0 at reduced pressure. A yield of 183g. or of theoretical of poly-4-vinylpyridinium chloroacetamide was obtained. Analysis of this product showed that it contained by weight 49.9% of carbon, 6.3% of hydrogen, 13.8% of nitrogen and 18.3% of chlorine compared with calculated for of 54.5%, 5.5%, 14.1% and 17.9%, respectively. 'Accordingly, the product consisted essentially of recurring units of the following structure:

II C( CHz-C-NH:

The product showed excellent antistatic properties when coated on thin wrapping materials and photographic films.

EXAMPLE 10 g. (0.95 mole) of poly-4-vinylpyridine }==l.38] were dissolved in 750 cc. of methanol by stirring at room temperature. g. (1 mole) of u-chloro-N,N-diethylacetamide were added to the viscous solution. This mixture was warmed in a steam, bath until water-soluble.

The viscous solution was precipitated into 4 liters of diethyl ether and the amber-colored polymer leached in fresh ether. The product was then dried at reduced pressure. The yield of polymeric quaternary salt product was g. or 60.7% of the theoretical value. Analysis showed that this product contained by weight 63.1% of carbon 7.1% of hydrogen, 10.7% of nitrogen and 10.2% of chlorine compared with calculated for C H N OCl of 6 1.3%, 7.4%, 11.0% and 13.9%, respectively. This result indicated that the product, poly-4- vinylpyridinium-o -chloro-N,N-diethylacetamide, consisted 95 of 'abont-73% by weightof recurring otmeronm; ing; structure;

the remainder f; the palms-molec le beia residualre: curring 4-vinylpyrldine units. The product showed good antistatic properties when coated on thin wrapping materials and photographic. films.

EXAMPLE 12,;

V the solution was then applied as a backing to a sheet oi cellulose acetate film base by means of a dip roller and dried. The film was then further coated on the reverse side with a suitable subbing layer and a gelatine-silver halide emulsion. The following table lists the polymeric salt, the solvent combination, the concentration of polymeric salt therein, thecoverage of the coating, and the conductivity and appearance, of the coated films.

,Iab l l Antlstatleeoatlng Qompposttloug Coated Film Solvent Combination-Wt. Antistatle Coating ticlvm tesa t Ratios conc nt atlonPoly-.

- a made Salt, Appearance Wt. Percent (levera e, Conductiv- Acetone Methanol Water 1 microityXlO- mho Broduct, oi vErr. 1- (POlY-lyQQiiOflYLfiVlD-Yl- '35 65- 0. 062 0.5 clear.

Ipyridlnlum chlorlde) 65 0.125 19.0 Do. .I I v 35 65 0.25 39.0 D0. Broduct oLEx. 2 (Poly-4 in lpyrldlnlum 70 30 0.5 0.15 D0. 'chloroacetymnlllde)" g 70 g 30 1.0 r 2.0 Do.

' 70 30 2.0 7.0 Do. Rroduetof Ex.,4;;(Boly-1-ethyl v nvlpyridtn 70 30 0.25 1.3 Do. ium chloroacetate) 30 70 0.25 5.9 Do. 60 0.25 5.6 Do. Product otEx. (Boly-l-octade 1-4 I yl; 60 0.25 8.0 Do. pyrldinlum chloroacetate).- I 40 60 0.5 19.0 Do. 40 60 1.0 53.0 Do. Product of Ex. 9,- (BolyA-vlnylpyrldinlum 70 30 0.25 1.0 Do. chloroaeetarnideLu, j. 30 70 0.25 1.6 Do. 1 60 0.25 1.2 Do i a 0.02? go. Brofiuct ot'Ex. 10. (-P0ly-4-.vinylpyrldlnlum-a;. 20 I 1* 0 1,0 4.3 Do. t fl q z 7"" 70 30 0.5 0.4 Do. V r w 70 so 1.0 i 2.1 Do. 70 so 2.0 91.0 Do. Ero duchotqEx.11.(Roly:i vlnyl lunn 70 30 0.5. 1.3 Do. chloro-N ethylacetanlllde) ig... 70 30 L0 0.0 Do. 70 30 1 2.0 18.0 Do.

EXAMPLE 11 5111.961 conductivities of the order greater than 10- 25 g. (0.238 mole) of poly-4- vinylpyridine were dissolved in 150 cc. of methanol by stirring at room temperature. 75 g. (0.38 mole) of .-chloro-N-ethylacetanilide were added and the mixture heated in a C. water bath until water-soluble. The viscous solution was precipitated into 4 liters of diethyl ether. The precipitated bufiwolored:polymeriwas the "dried: at reduced pres-. sure. The yield of poly-men ,tproduct was. 5.6. g. or 19%. ofthetheoretical: value.1,Analysis on the product showedrthat it contai-ned by weight;63.3-.% of carbon, 7;.2i%ofhydrogen, 8f;7% -ofnitrog en and 10.4% of ch10; compared with; calcula tedi 'for. cflH NgOclz or 6214-971, 63%;. l;2.-%L and 11.7%,.respectiyely; .resnlt indicated: that; the .product, 1 po1y-4'vinylpy'ndiniurn,-. u-chloro-N-ethylacet-anilide, consisted ofi approximately 89% of recurring units of the following structure:

mho have been found to alleviate difiiculties from static electricity generated in the normal handling of photographic film, itwill be seen fromthe above table that by use of the polymeric salts of the invention in appropriate concentrations and solvent combinations as coatings, films canbe prepared which are free from troublesome static effects.

The conductivity, measurements for the above table were carried out by placing two parallel electrodes on the film at: a fixed relative humidity of SOxpereent; these electrodes'are long compared to the distance between them, so as to avoid end effects. The observed reading is'divided ,by the distance between electrodes and multiplied by their length, to obtaint-he surface resistivity in ohms, the conductivity being the reciprocal thereof.

While the polymeric salts of the invention have been illustrated. primarily in connection with their use as anticompositions of the invention are also useful for renderstatic. coa i gs or' lightensit v P p cv fi m .w it

he. understood that coatings thereof are also efi'icacious in the prevention of static build up and adhesion when coated; on'nonesensitized surfaces such'as various naturalfand'synthetic wrapping materials.v Also, various fillers, dyes, softeners; etc. can be incorporated, if desired, into the cqatingcornpositions ofthe invention. In addition to these uses-filepolymericsalts and coating 18 a ernt x i e ater els. etstanti atie by rea n the ewith anctare; capable. of; f n g many? P asses as wettingzagentsliflhose polymeric salts that con:

auras-as vention vary in solubility depending upon the propor tion of quaternary salt units'contained therein, for ex-. ample, they are methanol-soluble, water-insoluble at somewhat less than 70% by weight of quaternized units but methanol-soluble, water-soluble for the salts containing 70 to approximately 100% by weight of quaternized units.

The processes for preparing the resinous quaternary. salts of the invention may also be modified to some ex: tent. For example, instead of precipitating the viscous solution or dope obtained in the quaternizing reaction by pouring into a non-solvent such as diethyl ether, advan: tageously the solution may be siphoned through .a tube (e.g. 8 mm. diameter) and run slowly into the non-solvent precipitating liquid, while mechanically shaking the end of the tube to form discrete droplets at the end of 'thetube, which then become transformed in falling through the precipitating liquid into porous half beads or granules said film having'in oneouter stratum thereof, a quaternary salt of a resinous C-vinylpyridine polymer consist' ing of not less than 70% by weight of quaternized, polymerized units of the general structure:

andnotmore than 30% by weight of non-quaternized, polymerized units of the general structure:

i i I "GHQ OH" wherein Y represents a member selected from the group consisting of a hydrogen atom and an alkyl radical of of polymeric salt that are easy to filter, wash and store,

and which are particularly well adapted for easy han: dling in subsequent uses of the polymeric salt beads or granules.

Although the invention is primarily concerned with" the saturated polymeric salts which are the most advantageous for antistatic coatings, certain other polymeric salts of an unsaturated character also have good anti,

static properties. The following examplev illustrates polymeric salts of the vinyl ester type.

EXAMPLE 13 50 g. (0.475 mole) of poly-4-vinylpyridine .were dissolved in 250 cc. of'methanol by stirring at'room temperature. Then 90 g. (0.75 mole) of vinyl chloroacetate were added to the viscous solution and this mixture was heated at 4050 C. for 24 hours, after which time the quaternary salt was precipitated from solution in 4 liters of diethyl ether. The brittle, amber solid: was leached in two changes of ether and dried over P 05 at reduced pressure. chloroacetate was 70 g. or equivalent to 77% of the theoretical value. The conductivity measurements by the aforementioned method of Example 12 were as follows;

The above data indicate that the polymeric salt of this example provides adequate conductivity to furnish protection from static efiects when coated onto the back side of film base. i w

In place of the vinyl chloroacetate in the ahove'ex ample, there'may be substituted a like amount of other vinyl esters including vinyl chloropropionate,. vinyl chlorobutyrate, etc. to give polymeric salts having generally similar antistatic properties.

What we claim is: 1. An antistatic photographic film comprising a-trans parent, flexible organic fihn support having -thereon at least one light-sensitive silver halide emulsicn 'layer, the

The yield of poly-4-vinylpyridinium vinyl,

1 to 4 carbon atoms, X represents a halogen atom and -A represents a member selected from the group consisting of (l) a monovalent radical R which represents a member selected from the group consisting of an alkyl radical of l to 4 carbons atoms, a phenyl radical, a

'hydroxyphenyl radical wherein the hydroxyl radicals do not exceedl', and an acetarnidophenyl radical, (2) a monovalent radical-OR; wherein R represents an alkyl radical 'of 1 to24 carbon atoms, and (3) a monovalent radical NR R wherein R is selected from the group ..consisting of a hydrogen atom and an alkyl radical of l to 4 carbon atoms and RE, is selected from the group consisting of a hydrogen atom, an alkyl radical of 1 to 4 carbon atornsand a phenyl radical.

2. An antistatic photographic film comprising a cellulose carhoxylic acid ester support having on one side thereon at least one light-sensitive silver halide emulsion layer and on the opposite side of the said support, a layer comprising a quaternated resinous 4-vinylpyridine polymer consisting of at least 70% by weight of quaternated, polymerized units of the general structure:

' -crr,-on- V and not more than 30% by weight of non-quaternated, polymerized 4 -vinylp'yridine units. 5 t 1 a 4. antistatic photographic film comprisinga cellulose-carboxylic acid ester support having on one side thereon at least one light-sensitivesilver halide emulsion- 13 layer-and on the opposite side of the said support, a layer comprising a quaternated resinous 4-vinylpyridine polymer consisting of at least 70% by weight of quaternated, polymerized units of the general structure:

N C( CH 3-OC1s a1 and not more than 30% by weight of non-quaternated, polymerized 4-vinylpyridine units.

5. An antistatic photographic film comprising a cellulose carboxylic acid ester support having on one side thereon at least one light-sensitive silver halide emulsion layer and on the opposite side of the said support, a layer comprising a quaternated resinous 4-vinylpyridine polymer consisting of at least 70% by Weight of quaternated, polymerized units of the general structure:

and not more than 30% by weight of non-quaternated, polymerized 4-vinylpyridine units.

6. An antistatic photographic film comprising a cellulose carboxylic acid ester support having on one side thereon at least one light-sensitive silver halide emulsion layer and on the opposite side of the said support, a layer comprising a quaternated resinous 4-vinylpyridine poly- 14 mer consisting of at least 70% by weight of quaternated, polymerized units of the general structure:

C( CHr-C-N and not more than 30% by weight of non-quaternated, polymerized 4-vinylpyridine units.

7. The antistatic photographic film according to claim 15 1 wherein the said support material is cellulose acetate.

8. The antistatic photographic film according to claim 2 wherein the said support is cellulose acetate. 9. The antistatic photographic film according to claim 3 wherein the said support is cellulose acetate.

10. The antistatic photographic film according to claim 4 wherein the said support is cellulose acetate.

11. The antistatic photographic film according to claim 5 wherein the said support is cellulose acetate.

12. The antistatic photographic film according to claim 25 6 wherein the said support is cellulose acetate.

References Cited in the file of this patent UNITED STATES PATENTS N O caHt 2,484,430 Sprague et al Oct 11, 1949 2,548,564 Sprague et a1. Apr. 10, 1951 2,612,446 Umberger Sept. 30, 1952 2,623,013 DAlelio Dec. 23, 1952 2,688,008 Chaney et al. Aug. 31, 1954 2,717,834 Saner Sept. 13, 1955 2,717,887 Saner Sept. 13, 1955 2,725,297 Morey Nov. 29, 1955 2,882,157 Thompson et a1. Apr. 14, 19 59. 

1. AN ANTISTATIC PHOTOGRAPHIC FILM COMPRISING A TRANSPARENT, FLEXIBLE ORGANIC FILM SUPPORT HAVING THEREON AT LEAST ONE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER, THE SAID FILM HAVING IN ONE OUTER STRATUM THEREOF, A QUATERNARY SALT OF A RESINOUS C-VINYLPYRIDINE POLYMER CONSISTING OF NOT LESS THAN 70% BY WEIGHT OF QUATERNIZED, POLYMERIZED UNITS OF THE GENERAL STRUCTURE: 